Printing ink containing a terpene modified phenol formaldehyde resin



Patented Oct. 28, 1952 fan-5,854 PRINTING INK CONTAINING A TE-RPENE MODIFIED PHEN :R sIN oL FOBMALDEHYDE John Pantin, Chicago, and Gordon-R. Mat

Quaker, .Wheaton, Ill., assignors to Sun'Chemical'Corporation, Long Island City, N. Y., a

corporation of Delaware a No Drawing. Application September 1-9,

Serial No. 114,918

9 Claims. ('01. 260-25) f f 1 The present invention relates to printinginks and, more particularly, to-printing-inks employing high boilingsolvents as the liquid medium thereof and adapted for quick drying'of the imprinted ink film by application of heat.

An object of the present invention is to provide printing inks employing high boiling solvents as the liquid medium thereof, which upon being printed as a film and subjected to high temperature drying conditions, furnishflhighly glossy prints. v v.

Another object of the present invention is to provide printing inks containingv gel-like compositions, which compositions are" substantially heat stable.

Another object of the present invention is to provide printing inks characterized by the resistance of imprinted films of such inks to paper penetration under the influence of hight'emperature conditions. v I

- Other objects of the present 'invention'will be apparent from the following description and apof highly volatile solvents whichevap'ora'te almost instantly upon application of the ink as a thin film upon a suitable surface. Where high boiling solvents are employed as the liquid medium of printing-inks, rapid drying-of the imprinted ink film is accomplished by the application of sufficient heating to the imprinted surface to eifect almost instantaneous evaporation of the solvent contained in the imprinted ink film without burning or otherwise adversely 'affecting the. imprinted material.

Printing inks containing such high boiling solvents asthe liquid medium thereof have obtained widespread use in high speed typographic printing, particularly in the field of magazine printing Where sharpness and clarity of reproduction are essential. Such characteristics are obtainable withinks of this'type due to the high press stability of these inks, such characteristic permittingthe use of largeink distributing systems' which distribute the ink evenly, smoothly and uniformly on its way from the ink fountain,

or reservoir, to the printing plate, thus insuring the application of a controlled and uniformly 'thick ink film upon the surface to" be printed. 11. orderto. ,e rapid d in o heimprin efd H ink film, theimprinte'd surface or material'-such as, for example, the paper web employed incontinuous rotary printing operations, is} ledfinto contactwith some suitable'heating means which instantly vaporizes the liquid solvent contained in the imprinted ink film, drying the saidfi-lrn and permitting the imprinted web to be immediately rewound, or to be passed'to a second printing unit for reverse side printing without danger-of offset; Such heating means may consist of heated roll ers over which theweb rides after printing, or it may consist of a' chamber wherein 'a series of gas fiamesQorgthe heat g'enerated'byjthe same, are directed'upon the surface of the rapidly movg ingweb, or it: may consist ofjany other heat furnishing means capable of instantly vaporizing the solvent in the'ink film without adversely an footing the imprinted surface. One v great disadvantage of the method of'quick drying inks as outlined above lies inthe fact that upon sub jecting the imprinted su'r'facefto a heat whichh's sufficiently intenseas to effect immediate ev'ap orationfof the solvent contained in'the'ink film and eifect drying of the ink film thereby; a' print is'obtained which is verym'uchlacking gloss aproperty highly desired in ordinary magazine printing. Exactlylwhy'it is that'the application of heat seems todeaden the apparent 'glossf'of the ink film is notknown with certainty, It may be that the intense heat causes the ink'ffill'n to penetrate into the paper to such anextent thatanyj gloss which ordinarilyfmight'ghave been obtained is lost. Or. it: may be that too great a penetrationYpfthe paper by the jfreshlyjmprinted film occurs between printingjanddry ing, to leave a sufficient amount ofink upon the paper surface. to withstand" the gloss' killing action of the heat. j g Y It has been thought that if some system --were devised whereby the extent" of the f paperpenetration of the imprinted ink film' couldbe reduced n that interval after printingand before application of heat thereto, the imprinte'd' inkffilm would remain on the surfacdofthe paper during the drying operation and thereforeretain mu'ch of the apparent gloss. of the ink. Tothis e'nd,

there havejbeen incorporated "into such -i-nk s vari- Ous jmaterials and compositions, which it' "was hoped, would withstand the, action o f th heat and thus resist destruction of the gloss of the print, either bypreventing excessivepaperfpenetration by the ink film under thejactionpftlie heat or by retaining the ink film in, such condition as to maintain the natural gloss: characteristics oftheink. Among; the various mate which been employed have had no'appreciable efiectin resisting the action of the heat insofar as the gloss of the finished print was concerned. Whatever the action of the heat upon the imprinted" ink film may have been, a print wasusually obtained which was extremely lifeless, fiat, and

lacking in gloss.

We have found, according to the present invention, that printing inks containing high boil ing solvents as the liquid medium thereof can be prepared which, upon being imprinted as a film which is subsequently subjected to rapid heat drying conditions while still in a wet orunset condition, furnish prints which exhibit a gloss atleast equalto that obtained when, the ink film is allowedto dry under normal air drying conditions.

The printing inks of the present invention comprise a .vehicle in which highjboiling aliphatic hydrocarbon'solvents constitute the liquid medium thereof and wherein a resinous material which is soluble in the said solvents constitutes the binder material thereof, and in which there isv included a gel-like composition consisting of a high boiling aliphatic hydrocarbon solvent, a high boiling aliphatic hydrocarbonsolvent soluble terpene-modified, phenol-formaldehyde resin and aluminum octoate, the latter material being present in suchgproportion as to, provide a substantially-stable gel-likecomposition,

The aliphatic hydrocarbon solvents employed in theinks of the present invention are those which are generally obtained from petroleum sources and may satisfactorily constitute anyof the higher boiling fractions thereof. The resinous binder of theseinks may be any of those resins which are soluble in' the said aliphatic hydrocarbon solvents and which are commonly employed in inks of the heat dryin type. It is understood that any of the coloring materials commonly utilized in printing inks may satisfactorily be incorporated in the inks of the present invention.

The gel-like compositions which comprise an essential part of the inks of the present invention contain a solvent which is of the same type and character as the solvent employed as the liquid medium of the said inks. The particular resin employed-in conjunction with aluminum octoate to provide the gel-like compositions is an isomerized terpene-modified phenol-formaldehyde oil-soluble and aliphatic hydrocarbon solventsoluble thermoplastic resin,manufactured and sold by Durez Plastics. and Chemicals Inc. under the name Durez 220. I The said resin has a melting point of approximately 286 F. 5 R,

an acid number of 17 to 22 and a specific gravity for example, 15%, of the above varnish an amount of aluminum octoate corresponding to between approximately 2% and 4% by weight of the total yarhish." The slurry thus formed is added to the remainder of the varnish at a temperature of approximately 150 F. and the temperature of the varnish is thereupon gradually raised to approximately 215 F. under agitation conditions and maintained thereat until a composition having somewhat of a gel-like consistency has been obtained. Agitation and heating of the above materials may satisfactorily be accomplished in a suitable mixing machine, such as a steam jacketeddough mixer, or similar mixing device.

Illustrative of heat drying compounds prepared according to theabove outlined process are the compositions corresponding to the following formula's.

Parts by Heat dry compound #1: weight Aliphatic hydrocarbon solvent (boiling hyde' resin u 43.65 w i sie ie,

"range 280 C.'-290 C.) 48.0 ,Terpene modified phenol formalde hyde resin 48.0 Aluminum octoate, 4.0

'1 100.0 Heat dry compound #3:

Aliphatic hydrocarbon solvent (boiling range 300 C.-310 C.) 58.5 Terpene modified phenol formaldehyde resin 39.0 Aluminum octoate 2.5

e 100.0 Heat dry compound #4:

Aliphatic hydrocarbon solvent (boiling L H range 250 C.-260 C.) v 43.0

Terpene modified phenol formaldehyde resin A 53.5 Aluminum octoate 3.5

The printing inks of the present invention may beprepared by any of the methods commonly utilized in the printing ink industry. For example, a vehicle may be prepared by effecting solution of a resin in a" high boiling aliphatic hydrocarbon solvent and the dry pigment may .ball mill' If it is desired to employ the pigment in the pulp state, such; as the press cake obtained in; the manufacture of lake colors, the pigment may be flushed into the ink vehicle to obtain dispersion of the same therein. Satisfactorily, the heat dry compound may then be incorporated into thepigmented vehicle thus prepared by mixing ,the heat dry -compound. therewith-untila smooth, homogeneous composition. has been 'obtained. If desired, the heat dry compound may first be incorporated in the ink vehicle and the pigmentadded later with milling, but such procedure is not preferred. To obtain the most satisfactory results with the inks of the present invention, the amount of heat dry compound in- 5 corporated' .into the inkcompositions of: the presentinvention shouldbe within the ran e of approximately 40%-'60%' by weight based u-pon the weight ofithe ink vehicle. Sincethe inkvehicles of: the inks of the present. invention usually con- .stitute from approximately 70% "by weig-ht to approximately 90% ,by weight -of-the--sai;d;-inks, although such a range should'notnecessarily be considered as limiting, :the -amountof :heat dry compound which may generally be incorporated into the inks of'the-present invention-may vary between the ranges of approximately 28% by weight and approximately: 56 by'weight based upon the total weight of the ink. I v

The following ink compositions-are illustrative of successful commercial inks--prepared--according to the present invention.

Example I:

. Benzidinecyellowpigment; 112. 6 Zinc resinate 24.5 Aliphatic hydrocarbon .solvent (boiling range 301C.%3l C 20;0 Heat dry compound #1 -1429 'jExampleiI: v

.;Ph1ox ine red pigmentg 15:7 Calcium resinatedlithol red pigment"- 32 jlEentaerythritolaabietic acid resin 'l2:9'

Example 111:

Peacock :blue --;pigment s- 2610 5Pentacrythritoleabieticvacid:resinc ."Aliphatic; hy rocarbon solvent. (be. .p

z-range. 3280i C.-,'299,,C.)

Prints made by imprinting the printing ink of the present invention as a film upon a paper surface which is then immediately subjected to the usual heat drying operations exhibit a high gloss and smooth finish. There is no apparent deterioration of the ink film under such heating conditions as is usually had with the commonly employed heat-set inks.

Exactly why such desirable results are obtained by the employment of the gel-like compositions setforth above, is

not known with certainty but it is evident that such compositions are substantially stable under the intense-temperatures employed in the heat drying operationsto-the extent of preventing deterioration of the inkfilm upon the immediate evaporation of the solventcontained therein, or at leastto theextent of arresting paper penetration by the imprinted ink film due-to-the-heat drying. Furthermore; the trapping qualities of the inks -of the present invention, that is, the

ability Y to j print successive colors one upon a the other while the previously ilnprir'ited film is still -in an-u-nset'condition, are greatly superior to thoseof conventional heat dryinks. This is due tothe fact that printing inks containing the heat dry compounds of the present inventionare generally more stable toward the heat generated by1the printing press during the printingoperaof a terpene-modified phenol-formaldehyderesin and aluminum octoate in the preparation or I the said compositions which provide such desirable characteristics to the inks of, the present inventionyfor'other ge1'-1ike compositions have been employed in heat-set printi g 'inks w thcutcb taining' such; results. Nor has ,the; incorporation intoiheat-set 'inks :of gcl-'1ike compositions em- 'plo ying other, aluminurn ,;s alts as-the gel-lingagent .of the said compositions, such asthe aluminum salts of; the higher fatty -;acids, provid ed, adequate protection against deterioration of the imprinted ink "film under high temperature conditions. Whatever the reason' for theeifect of the heat dry compounds upon the printinginks of the present invention may be, it has been" found thata compositionprepared accordingto the present invention, formaldehyde, resin, a high boiling: aliphatic. .hy-

employing I a 'terpene-modified phenoldrocarbon solvent, and-aluminumoct a-te-in the 'proportionsas heretoioreset out, and which composition possesses-gel-like characteristics, when I incorporated into ..a printing ink or printing ink vehicle such as are set'forthhereinbeiore will impart to the completed -ink; ,the characteristics of lessenedvpaper penetration ofthe imprinted ink film and agreaterglossand'finishyto'the said ink film, after evaporation-of the solventtherefrom by heating.

I 'Wl'1i1e' the above products ,and processes of, preparing the same constitute preferred embodiments of the present invention, changes may be made therein without departing from the scope of the invention as defined in the appended claims.

What is claimed is:

1. A vehicle for a printing ink comprising zinc resinate and a high boiling aliphatic hydrocarbon solvent therefor, said solvent having a boiling point not lower than approximately 240 C., and including from about 40% by weight to about 60% by weight based upon the weight of the said vehicle of a gel-like composition consisting of a high boiling aliphatic hydrocarbon solvent soluble terpene-modified phenol-formaldehyde resin, a high boiling aliphatic hydrocarbon solvent having a boiling point not lower than approximately 240 C. and approximately 2% to 4% by weight based upon the weight of the said composition of aluminum octoate. 3

V 2. A vehicle for a printing ink comprising a pentaeiythritol-abietic acid resin and a high boiling aliphatic hydrocarbon solvent therefor, said solvent having a boiling point not lower than approximately 240 0., and including from about 40% by weight to about 60% by weight based uponthe weight of the said vehicle of a gel-like composition consistin of a high boiling aliphatic hydrocarbon solvent soluble terpene-modified phenol-formaldehyde resin, a high boiling aliphatic hydrocarbon solvent having a boiling point not lower than approximately 240 0., and approximately 2% to 4% by weight based upon the weight of the said composition of aluminum octoate. I

3. A vehicle for a printing ink comprising calcium resinate and a high boiling aliphatic hydrocarbon solvent therefor, said solvent having a boiling point not lower than approximately 240 C., and including from about 40% by weight to about 60% by weight based upon the weight of the said vehicle of a gel-like composition consisting of a high boiling aliphatic hydrocarbon solvent soluble terpene-modified phenol-formaldehyde resin, a highboiling aliphatic hydrocarbon solvent havin a boiling point not lower than aping a boiling point not lower than approximately 240 C., and approximately 2% to 4% by weight based upon the weight of the said composition of aluminum octoate.

5. A printing ink comprising coloring material dispersed in a vehicle comprising pentaerythritolabietic acid resin and a high boiling aliphatic hydrocarbon solvent therefor, said solvent having a boiling point not lower than approximately 240 C., and including from approximately 28% by weight to about 56 by weight based upon the Weight of the ink of a gel-like composition consisting of a high boiling aliphatic hydrocarbon solvent soluble terpene-modified phenol-formaldehyde resin, ahigh boiling aliphatic hydrocarbon solvent having a boiling point not lower than approximately 240 0., and approximately 2% to 4% by weight based upon the weight of the said composition of aluminum octoate.

v6. A printing ink comprising coloring material dispersed in a vehicle comprising calcium resinate and a high boiling aliphatic hydrocarbon solvent therefor, said solvent having a boiling point not lower than approximately 240 C., and including from approximately 28% by weight to about 56% by weight based upon the Weight. of the ink of a gel-like composition consisting of a high boiling aliphatic hydrocarbon solvent soluble terpenemodified phenol-formaldehyde resin, a high boiling aliphatic hydrocarbon solvent having a boiling point not lower than approximately 240 C., and approximately 2% to 4% by Weight based upon the weight of the said composition of aluminum octoate.

7. A substantially-heat stable-gel-like composition consisting of from approximately to 60 parts by weight of a terpene-modified phenolformaldehyde resin, 70 to parts by weight of high boiling aliphatic hydrocarbon solvent having a boiling point not lower than approximately 240 0., and between approximately 2% to 4% by weight of the said composition of aluminum octoate.

8. A vehicle for a printing ink comprising a resinous binder selected from the group consisting of metallic resinates and rosin esters, and a high boiling aliphatic hydrocarbon solvent therefor, said solvent having a boiling point not lower than approximately 240 C., and including from about 40% by weight to about by weight based upon the weight of the said vehicle of a gel-like composition consisting of a high boiling aliphatic hydrocarbon solvent-soluble terpene-modified phenol-formaldehyde resin, a high boiling aliphatic hydrocarbon solvent having a boiling point not lower than approximately 240 0., and approximately 2% to 4% by weight of the said composition of aluminum octoate.

9. A printing inkcomprising'coloring material dispersed in a vehicle comprising a resinousbinder selected from the group consisting of metallic resinates and rosin esters, and a high boiling aliphatic hydrocarbon solvent therefor, said solvent having a boiling point not lower than approximately 240 C., and including from approximately 28 by weight to about 56% by weight based upon No references cited. 

8. A VEHICLE FOR A PRINTING INK COMPRISING A RESINOUS BINDER SELECTED FROM THE GROUP CONSISTING OF METALLIC RESINATES AND ROSIN ESTERS, AND A HIGH BOILING ALIPHATIC HYDROCARBON SOLVENT THEREFOR, SAID SOLVENT HAVING A BOILING POINT NOT LOWER THAN APPROXIMATELY 240* C., AND INCLUDING FROM ABOUT 40% BY WEIGHT TO ABOUT 60% BY WEIGHT BASED UPON THE WEIGHT OF SAID VEHICLE OF A GEL-LIKE COMPOSITION CONSISTING OF A HIGH BOILING ALIPHATIC HYDROCARBON SOLVENT-SOLUBLE TERPENE-MODIFIED PHENOL-FORMALDEHYDE RESIN, A HIGH BOILING ALIPHATIC HYDROCARBON SOLVENT HAVING A BOILING POINT NOT LOWER THAN APPROXIMATELY 240* F., AND APPROXIMATELY 2% TO 4% BY WEIGHT OF THE SAID COMPOSITION OF ALUMINIUM OCTOATE. 